Functionalized 4- and 5-vinyl substituted regioisomers of 1, 2, 3-triazoles via 1, 3-dipolar cycloaddition and polymers thereof

ABSTRACT

The present invention provides novel functionalized mixtures 4- and 5-vinyl substituted regioisomers of 1,2,3-triazoles via 1,3-dipolar cycloaddition. Functionalized alkyne moieties with a terminal alcoholic functionality are reacted with functionalized organic moieties with a terminal leaving group and an azide to provide an alcoholic functionalized mixture of 4- and 5-substituted regioisomers of 1,2,3-triazole moieties. The mixture may be converted to a wide variety of useful functionalized mixtures of 4- and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties, which in turn can be converted to a wide variety of useful polymers The novel alcoholic functionalized mixtures of 4- and 5-substituted regioisomers can be separated by chromatography to provide the purified 4- and 5-alcoholic functionalized substituted 1,2,3-triazole moieties. The novel compounds of the invention can be employed in a wide variety of compositions (Formulae (I), (II)); wherein R 1 , R 2 , R 3 , and R 4 , are defined herein.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention provides novel functionalized 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazoles via 1,3-dipolarcycloaddition. The novel compounds are prepared by the ligation ofazides and alkynes using 1,3-dipolar cycloaddition reactions.Functionalized alkyne moieties with a terminal alcoholic functionalityare reacted with functionalized organic moieties with a terminal leavinggroup and an azide to provide an alcoholic functionalized mixture of 4-and 5-substituted regioisomers of 1,2,3-triazole moieties. The mixturemay be converted to a wide variety of useful functionalized mixtures of4- and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties,which in turn can be converted to a wide variety of useful polymers. Thenovel alcoholic functionalized mixtures of 4- and 5-substitutedregioisomers can be separated by chromatography to provide the purified4- and 5-alcoholic functionalized substituted 1,2,3-triazole moieties.The novel mixtures of 4- and 5-vinyl substituted regioisomers can alsobe separated by chromatography to provide the purified 4- and 5-vinylsubstituted 1,2,3-triazole moieties. The novel compounds of theinvention can be employed in a wide variety of compositions.

2. Description of Related Art

The ligation of azides and alkynes using a 1,3-dipolar cycloadditionreaction (azide/alkyne chemistry) has been described in United Statespatent application 2005/0222427 and in EP patent 1507769. The reactioninvolves ligation of azides and alkynes in solution using a copper (I)salt catalyst [Cu(I)], or a copper (II) salt catalyst [Cu(II)] in thepresence of a reducing agent, such as sodium ascorbate, to providetriazole polymer moieties under ambient conditions (“click reaction”),see H. C. Kolb, M. G. Finn and K. B. Sharpless, Angew. Chem. Int. Ed.2001, 40, 2004-2021. The advantage of the copper catalyzed method overthe uncatalyzed method is said to be rate acceleration and exclusive1,4-regio selectivity. These references also describe azide/alkyneligation chemistry for the preparation of triazole polymer moieties asmetal adhesives using Cu(I) catalysts, prepared by reducing Cu(II) or byoxidizing copper metal to Cu(I) in situ, see D. D. Diaz, S. Punna, P.Holzer, A. K. Mcpherson, K. B. Sharpless, V. V. Fokin, M. G. Finn, J.Polym. Sci: Part A: Polym. Chem. 2004, 42, 4392-4403. References thatdescribe the preparation of vinyl-1,2,3-triazole moieties include G.Wouters, et al., Makromol. Chem. 183 1861-1868 (1982); Raymond J.Thibault, et al., J. Am. Chem. Soc. 2006, 128, 12084-120585; and KenichiTakizawa, et al., J. of Polym. Sci.: Part A: Polym. Chem., Vol. 46,2897-2912 (2008).

The copper catalyzed azide/alkyne chemistry requires relatively mildreaction conditions that are not sensitive to air or moisture incontrast to the conditions used in radical polymerizations that areoften inhibited by oxygen, leading to incomplete polymerization andreduced yield. Nevertheless, the copper catalyzed azide/alkyne chemistryreactions require the disposal of the catalyst and/or solvent, whichadds steps to the synthetic method. It would advantageous to have amethod that did not require removal of a catalyst or organic solvent.

SUMMARY OF THE INVENTION

The present invention provides a wide variety of novel alcoholicfunctionalized 4- and 5-substituted regioisomers of 1,2,3-triazolemoieties, which may be converted to useful functionalized 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole moieties. The functionalized4- and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties maybe converted to a wide variety of useful polymers. The novel compoundsof the invention can be employed in a wide variety of compositions, suchas adhesive, coating, encapsulation, personal care, oilfield, membrane,agricultural, and cleaning compositions.

In one embodiment, the present invention provides an alcoholic mixtureof 4- and 5-substituted regioisomers of 1,2,3-triazole moieties.Preferably, the mixture is represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.

The mixture may also be represented by the structure:

wherein R₁ and R₂ are as defined above and R₅ is selected from the groupconsisting of functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; and x is an integer ranging from 1 toabout 500.

In another embodiment, the present invention provides an 4-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from2 to about 500.

In another embodiment, the present invention provides an 5-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

The 5-alcoholic substituted 1,2,3-triazole moiety may also berepresented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from1 to about 500.

In another embodiment, the present invention provides a mixture of 4-and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties.Preferably, the mixture is represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

The mixture may also be represented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from1 to about 500.

In another embodiment, the present invention provides a 4-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from2 to about 500.

In another embodiment, the present invention provides a 5-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

The 5-vinyl substituted 1,2,3-triazole moiety may also be represented bythe structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from1 to about 500.

In another embodiment, the present invention provides a homopolymer of amixture of 4- and 5-vinyl substituted regioisomers of 1,2,3-triazolemoieties. Preferably, the homopolymer is represented by the structure:

wherein R₁, R₂, R₃, R₄ are as defined above and y is an integer rangingfrom 2 to about 10,000.

In another embodiment, the present invention provides a homopolymer of a5-vinyl substituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₃, R₄ are as defined above and y is an integer rangingfrom 2 to about 10,000.

In another embodiment, the present invention provides a non-homopolymerof a mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties with a different polymerizable reactant moiety,wherein the non-homopolymer is a random, blocked, or alternatingpolymer. Preferably, the non-homopolymer is represented by thestructure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂, R₃, R₄ are as defined above and y and z are integers independentlyranging from about 2 to about 10,000, wherein the non-homopolymer is arandom, blocked, or alternating polymer.

Preferably, M is based upon a different polymerizable reactant moietyselected from the group consisting of anhydrides, vinyl pyrrolidones,vinyl caprolactams, acrylates, styrenes, maleimides, maleates,fumarates, cinnamyls, vinyl imidazoles, vinyl pyridines, vinyl acetates,acrylamides, vinyl sulfones, vinyl carbonates, vinyl silanes, vinylacrylamides, allyl alcohols, vinyl ethers, and mixtures thereof.

In another embodiment, the present invention provides a non-homopolymerof a 4-vinyl substituted 1,2,3-triazole moiety with a differentpolymerizable reactant moiety, wherein the non-homopolymer is a random,blocked, or alternating polymer, wherein the non-homopolymer isrepresented by the structure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂, R₃, and R₄ are as defined above and y and z are integersindependently ranging from about 2 to about 10,000, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

In another embodiment, the present invention provides a non-homopolymerof a 5-vinyl substituted 1,2,3-triazole moiety with a differentpolymerizable reactant moiety, wherein the non-homopolymer is a random,blocked, or alternating polymer, wherein the non-homopolymer isrepresented by the structure:

wherein M is based upon a different polymerizable reactant moiety,wherein R₁, R₂, R₃, R₄ are as defined above and y and z are integersindependently ranging from about 2 to about 10,000, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides a new vinyl monomer family, whichcombines the desirable features of thermal and chemical stability whileproviding functional versatility. Vinyl triazole monomers are asignificant advance beyond classic vinyl monomers derived from styrenic,acrylate, or α-olefin-based monomer systems. The invention demonstratesthe utility of cycloaddition of azides and alkynes resulting in uniquevinylic triazole monomers. This utility is supported by the benign(environmentally friendly) character of cycloaddition reactionconditions, functional group tolerance, quantitative yields andrelevance to a broad range of applications. These applications encompassadhesive, coating, encapsulation, personal care, oilfield, membrane,agricultural, and cleaning compositions. As found in styrenics, vinylpyridines, and acrylates, vinyl-1,2,3-triazoles possess attractivefeatures including stability, aromaticity, polarity, and versatilitywith substitutions at N-1. This new vinyl monomer family may be employedto yield novel vinyl triazole homopolymers and non-homopolymers with,for example, anhydrides, vinyl pyrrolidones, vinyl caprolactams,acrylates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinylimidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinylsulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allylalcohols, vinyl ethers, itaconic anhydrides, and citraconic anhydrides.

As used herein, the following terms have the meanings set out below.

The term “alkyne moiety” refers to an alkyne group, which may beattached to an unsubstituted or substituted alkyl, cycloalkyl, alkenyl,and aryl groups, wherein any of the before mentioned groups may bepresent with or without heteroatoms. The alkyl and alkenyl groups may bebranched or unbranched (straight-chain). Preferably, the alkyl andalkenyl groups are C₁-C₆₀, more preferably C₁-C₃₆, and most preferablyC₁-C₁₈ groups. Cycloalkyls (closed rings) include cyclopentane,cyclohexane, cycloheptane, and the like. Aryl groups include benzenes,naphthalenes (2 rings), and anthracenes (3 rings), and the like.

The symbol of a “bond to the middle of a vinyl group” means that thebond can be attached to either side of the vinyl group and generallymeans that the structure is referring to a mixture of isomers. Forexample, in the structure below:

the vinyl group containing R₁ and R₂ can be attached to either the 4 orthe 5 position of the 1,2,3-triazole moiety.

The term “direct bond’ means that the group can be nothing.

The term “free radical addition polymerization initiator” refers to acompound used in a catalytic amount to initiate a free radical additionpolymerization. The choice of initiator depends mainly upon itssolubility and its decomposition temperature.

The term “functionalized mixture of 4- and 5-vinyl substitutedregioisomers of 1,2,3-triazole moieties” refers to mixtures of1,2,3-triazole moieties substituted with a vinyl group at the 4 and 5position on the 1,2,3-triazole. Some non-limiting examples of structuresof functionalized mixtures of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties include:

The term “halogen” refers to chloro, bromo, iodo and fluoro, and ispreferably bromo or chloro.

The term “heteroatom” refers to atoms such as oxygen, nitrogen, sulfur,and phosphorous.

The term “homopolymer” refers to a polymer formed from a single monomer.

The term “inert solvent” refers to a solvent that does not interferechemically with the reaction.

The term “leaving group” refers to any group that can be displaced by anazide ion. Nonlimiting examples include halogens, silyl groups, tosylgroups, and mesyl groups.

The term “ligation” refers to an act of uniting or connecting two ormore starting materials or reactants.

The term “non-homopolymer” refers to a polymer formed from two or moremonomers and includes essentially all polymers that are nothomopolymers. Nonlimiting examples of non-homopolymers includecopolymers, terpolymers, tetramers, and the like, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

The terms “mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties”, “4-vinyl substituted regioisomers of1,2,3-triazole moieties”, and “5-vinyl substituted regioisomers of1,2,3-triazole moieties” refer to vinyl substituted 1,2,3-triazolemoieties having, for example, the structure shown below for the mixtureof 4- and 5-vinyl substituted regioisomers:

The configuration of the R₁ and R₂ groups on the vinyl bond is not meantto suggest any particular type of stereoisomerism about the double bond.Traditionally, double bond stereochemistry was described as either cis(on this side) or trans (across), in reference to the relative positionof substituents on either side of the double bond. IUPAC adopted a morerigorous system wherein the substituents at each end of the double bondare assigned priority based on their atomic number. If the high prioritysubstituents are on the same side of the bond, it is assigned Z(zusammen, together). If they are on opposite sides, it is E (entgegen,opposite). The structures of the vinyl substituted regioisomers of1,2,3-triazole moieties referred to in the present invention can eitherbe in the E or Z configuration, or mixtures thereof.

The term “monomer” refers to the repeat units comprising a polymer. Amonomer is a small molecule that chemically bonds to other monomers toform a polymer.

The term “organic moiety” refers to an unsubstituted or substitutedalkyl, cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be present with or without heteroatoms. The alkyland alkenyl groups may be branched or unbranched (straight-chain).Preferably, the alkyl and alkenyl groups are C₁-C₆₀, more preferablyC₁-C₃₆, and most preferably C₁-C₁₈ groups. Cycloalkyls (closed rings)include cyclopentane, cyclohexane, cycloheptane, and the like. Arylgroups include benzenes, naphthalenes (2 rings), and anthracenes (3rings), and the like.

The term “personal care composition” refers to such illustrativenon-limiting compositions as skin, sun, oil, hair, cosmetic, andpreservative compositions, including those to alter the color andappearance of the skin. Potential personal care compositions include,but are not limited to, polymers for increased flexibility in styling,durable styling, increased humidity resistance for hair, skin, and colorcosmetics, sun care water-proof/resistance, wear-resistance, and thermalprotecting/enhancing compositions.

The term “polymer” refers to a large molecule (macromolecule) composedof repeating structural units (monomers) connected by covalent chemicalbonds.

The term “x” refers to an integer commonly used in polymers and denotesthe number of repeating units of each monomer. In general, x in thepresent invention is about 1 to about 500, preferably from about 2 toabout 500, and more preferably from about 1 or 2 to about 400.

The terms “y” and “z” refer to integers commonly used in polymers anddenote the number of repeating units of each monomer. In general, y andz in the present invention are independently from about 2 to about10,000, preferably from about 100 to about 10,000, and more preferablyfrom about 1,000 to about 10,000.

As set out above, the present invention provides a wide variety of novelalcoholic functionalized 4- and 5-substituted regioisomers of1,2,3-triazole moieties, which may be converted to useful functionalized4- and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties. Thefunctionalized 4- and 5-vinyl substituted regioisomers of 1,2,3-triazolemoieties may be converted to a wide variety of useful polymers. Thenovel compounds of the invention can be employed in a wide variety ofcompositions, such as adhesive, coating, encapsulation, personal care,oilfield, membrane, agricultural, and cleaning compositions.

In one embodiment, the present invention provides an alcoholic mixtureof 4- and 5-substituted regioisomers of 1,2,3-triazole moieties.Preferably, the mixture is represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.

The mixture may also be represented by the structure:

wherein R₁ and R₂ are as defined above and R₅ is selected from the groupconsisting of functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; and x is an integer ranging from 1 toabout 500.

In another embodiment, the present invention provides an 4-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from2 to about 500.

In another embodiment, the present invention provides an 5-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

The 5-alcoholic substituted 1,2,3-triazole moiety may also berepresented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from1 to about 500.

In another embodiment, the present invention provides a mixture of 4-and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties.Preferably, the mixture is represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

The mixture may also be represented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from1 to about 500.

In another embodiment, the present invention provides a 4-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from2 to about 500.

In another embodiment, the present invention provides a 5-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

The 5-vinyl substituted 1,2,3-triazole moiety may also be represented bythe structure:

wherein R₁, R₂, R₅ are as defined above and x is an integer ranging from1 to about 500.

In another embodiment, the present invention provides a homopolymer of amixture of 4- and 5-vinyl substituted regioisomers of 1,2,3-triazolemoieties. Preferably, the homopolymer is represented by the structure:

wherein R₁, R₂, R₃, R₄ are as defined above and y is an integer rangingfrom 2 to about 10,000.

In another embodiment, the present invention provides a homopolymer of a5-vinyl substituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₃, R₄ are as defined above and y is an integer rangingfrom 2 to about 10,000.

In another embodiment, the present invention provides a non-homopolymerof a mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties with a different polymerizable reactant moiety,wherein the non-homopolymer is a random, blocked, or alternatingpolymer. Preferably, the non-homopolymer is represented by thestructure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂, R₃, R₄ are as defined above and y and z are integers independentlyranging from about 2 to about 10,000, wherein the non-homopolymer is arandom, blocked, or alternating polymer.

In another embodiment, the present invention provides a non-homopolymerof a 4-vinyl substituted 1,2,3-triazole moiety with a differentpolymerizable reactant moiety, wherein the non-homopolymer is a random,blocked, or alternating polymer, wherein the non-homopolymer isrepresented by the structure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂, R₃, and R₄ are as defined above and y and z are integersindependently ranging from about 2 to about 10,000, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

In another embodiment, the present invention provides a non-homopolymerof a 5-vinyl substituted 1,2,3-triazole moiety with a differentpolymerizable reactant moiety, wherein the non-homopolymer is a random,blocked, or alternating polymer, wherein the non-homopolymer isrepresented by the structure:

wherein M is based upon a different polymerizable reactant moiety,wherein R₁, R₂, R₃, and R₄ are as defined above and y and z are integersindependently ranging from about 2 to about 10,000, wherein thenon-homopolymer is a random, blocked, or alternating polymer.

The synthesis of the functionalized mixtures of 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole moieties is a three-stepmethod. Multiple chemical transformations occur in solution leading tothe desired functionalized mixtures of 4- and 5-vinyl substitutedregioisomers of 1,2,3-triazole moieties. In the first step, conditionsfor preparation of the triazole intermediate are environmentallyfriendly. For example, the reaction of an alkyne moiety with a terminalalcoholic functionality, such as 2-methylbut-3-yn-2-ol, sodium azide andan organic moiety with a terminal leaving group, such as an alkyl oraryl halide, is carried out in an aqueous medium without catalyst(s).Following in-situ generation of the azide derivative (displacement ofthe leaving group by the azide ion), a triazole “nucleus” is formed (1,3cycloaddition of the azide to the alkyne) and isolated as an alcoholicfunctionalized mixture of 4- and 5-substituted regioisomers of1,2,3-triazole moieties. Water is then removed from the alcoholic1,2,3-triazole moieties and, in the third step, the triazoleintermediates can then be readily dehydrated with, for example,phosphorus oxychloride in the presence of pyridine, triethyl amine, orother bases, or alternatively by simply heating the mixture. Thisreaction delivers a high yield of the desired N-1 substituted 4- and5-vinyl substituted regioisomers of 1,2,3-triazole moieties. Anattractive feature of this synthetic approach is the versatilityafforded by the wide variety of alkyl/aryl halide starting reagentsavailable. Thus, a wide variety of functionalized mixture of 4- and5-vinyl substituted regioisomers of 1,2,3-triazole moieties with variousN-1 substituents can be readily obtained. The functionalized mixtures of4- and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties canbe converted to a wide variety of useful polymers. The novel alcoholicfunctionalized mixtures of 4- and 5-substituted regioisomers can beseparated by chromatography to provide the purified 4- and 5-alcoholicfunctionalized substituted 1,2,3-triazole moieties. The novel mixturesof 4- and 5-vinyl substituted regioisomers can also be separated bychromatography to provide the purified 4- and 5-vinyl substituted1,2,3-triazole moieties. The novel compounds of the invention can beemployed in a wide variety of compositions.

The alkyne moiety may be an unsubstituted or substituted alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be present with or without heteroatoms. Preferably,the alkyne moiety is selected from the group consisting of2-methyl-3-butyn-2-ol, propargyl alcohol, but-3-yn-2-ol.3,6-dimethyl-4-octyne-3,6-diol, 1-phenyl-1-hexyn-3-ol,1-phenyl-4-methyl-1-pentyn-3-ol, 7-methoxy-3,7-dimethyl-oct-1-yn-3-ol,3,8 dihydroxy-3,8-dimethyl-4,6-decadiyne,1-trimethylsilanylethynyl-cyclohexanol, 1-phenyl-3-pentyn-2-ol,4-bromo-2-methyl-3-butyn-2-ol, 2-(2-fluorophenyl)-3-butyn-2-ol,2-(4-fluorophenyl)-3-butyn-2-ol, 2-(3-fluorophenyl)-3-butyn-2-ol,2,7-dimethyl-3,5-octadiyne-2,7-diol,2,6-dimethyl-oct-2-en-7-yne-1,6-diol, (S)-(−)-3-butyn-2-ol,(R)-(+)-3-butyn-2-ol, and 3-pentyn-2-ol. More preferably, the alkynemoiety is 2-methyl-3-butyn-2-ol.

The organic moiety with a terminal leaving group may be an unsubstitutedor substituted alkyl, cycloalkyl, alkenyl, and aryl groups, wherein anyof the before mentioned groups may be present with or withoutheteroatoms. Preferably, the organic moiety is selected from the groupconsisting of 1-bromooctane, methyl-3-bromopropionate, 2-chloroethanol,2-(2-chloroethoxy)ethanol, (dimethylamino)ethylchloride,3-chloro-1-propene, 2-chloroacetamide, acetyl chloride, 1-chloropropane,chloromethyl octyl ether, bromoethane, bromoacetonitrile,3-bromo-1-pentene, 2-bromopropane, 3-bromofuran, and 2-bromoimidazole.More preferably, the organic moiety is selected from the groupconsisting of 1-bromooctane, methyl-3-bromopropionate, 2-chloroethanol,2-(2-chloroethoxy)ethanol, and (dimethylamino)ethylchloride.

The terminal leaving group in the organic moiety may be selected fromthe group consisting of halogens, silyl groups, tosyl groups, and mesylgroups. Preferably, the leaving group is a halogen. More preferably, theleaving groups are chloro or bromo.

The dehydrating agent may be selected from the group consisting ofPOCl₃, acetic acid, nitric acid, sulfuric acid, and molecular sieves.

The alcoholic mixture of 4- and 5-substituted regioisomers of1,2,3-triazole moieties is preferably represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

Preferably, the alcoholic functionalized mixture of 4- and 5-substitutedregioisomers of 1,2,3-triazole moieties may be selected from the groupconsisting of:

More preferably, the alcoholic functionalized mixture of 4- and5-substituted regioisomers of 1,2,3-triazole moieties is:

The functionalized mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties is preferably represented by the structure:

wherein R₁, R₂, R₃, and R₄ are as defined above.

Preferably, the functionalized mixture of 4- and 5-vinyl substitutedregioisomers of 1,2,3-triazole moieties may be selected from the groupconsisting of:

More preferably, the functionalized mixture of 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole moieties may be selected fromthe group consisting of:

Most preferably, the functionalized mixture of 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole moieties is:

In another embodiment, the present invention provides a homopolymer of amixture of 4- and 5-vinyl substituted regioisomers of 1,2,3-triazolemoieties. Preferably, the homopolymer is represented by the structure:

wherein R₁, R₂, R₃, R₄ are as defined above and y is an integer rangingfrom 2 to about 10,000.

In another embodiment, the present invention provides a homopolymer of a5-vinyl substituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, R₃, R₄ are as defined above and y is an integer rangingfrom 2 to about 10,000.

The functionalized mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties may be polymerized with a differentpolymerizable reactant moiety to form a non-homopolymer. Preferably, thedifferent polymerizable reactant moiety may be selected from the groupconsisting of anhydrides, vinyl pyrrolidones, vinyl caprolactams,acrylates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinylimidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinylsulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allylalcohols, vinyl ethers, and mixtures thereof.

Illustrative, non-limiting examples of anhydrides include maleicanhydride, phthalic anhydride, lauric anhydride, pyromellitic anhydride,trimellitic anhydride, hexahydrophthalic anhydride;hexahydropyromellitic anhydride, hexahydrotrimellitic anhydride,itaconic anhydrides, citraconic anhydrides, and mixtures thereof.

More preferably, the different polymerizable reactant moiety may beselected from the group consisting of:

wherein R₁ and R₂ are as defined above.

Most preferably, the different polymerizable reactant moiety is selectedfrom the group consisting of:

The non-homopolymer may be selected from the group consisting of:

wherein y and z are integers independently ranging from about 2 to about10,000.

The present invention also provides a two-part composition comprising afirst part and a second part wherein (1) the first part comprises afunctionalized mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties comprising: (a) reacting a first reactant havinga functionalized alkyne moiety with a terminal alcoholic functionalityand a second reactant having an unsubstituted or substituted organicmoiety with a terminal leaving group with sodium azide in water, in theabsence of a catalyst or an organic solvent, to provide an alcoholicfunctionalized mixture of 4- and 5-substituted regioisomers of1,2,3-triazole moieties; (b) removing the water from the mixture in step(a); and (c) dehydrating the alcoholic functionalized mixture of 4- and5-substituted regioisomers of the 1,2,3-triazole moieties from step (b)with a dehydrating agent or by heating the mixture to provide afunctionalized mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties; and (2) the second part comprises apolymerizable reactant moiety, which can be the same as thefunctionalized mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties of the first part or a different polymerizablereactant moiety; wherein the first reactant and the second reactant ofthe two-part composition are admixed under polymeric conditions to forma polymeric moiety.

The different polymerizable reactant moiety in the second part may beselected from the group consisting of anhydrides, vinyl pyrrolidones,vinyl caprolactams, acrylates, styrenes, maleimides, maleates,fumarates, cinnamyls, vinyl imidazoles, vinyl pyridines, vinyl acetates,acrylamides, vinyl sulfones, vinyl carbonates, vinyl silanes, vinylacrylamides, allyl alcohols, vinyl ethers, and mixtures thereof.Suitable examples of these different polymerizable reactant moieties areas described above.

The present invention also provides an adhesive, coating, encapsulation,personal care, oilfield, membrane, agricultural, and cleaningcompositions comprising the above-described homopolymer. The presentinvention also provides an adhesive, coating, encapsulation, personalcare, oilfield, membrane, agricultural, and cleaning compositionscomprising the above-described non-homopolymer. The present inventionalso provides an adhesive, coating, encapsulation, personal care,oilfield, membrane, agricultural, and cleaning compositions comprisingthe above-described two-part composition. These polymers may be used inany industrial field. It is of particular use for electronic,electrical, opto-electronic, and photo-electronic applications. Suchapplications include die attach adhesives, underfill encapsulants,antennae for radio-frequency identification (RFID), via holes, filmadhesives, conductive inks, circuit board fabrication, other laminateend uses, and other uses with printable electronics.

Because the method of the present invention does not employ a catalyst,the method provides functionalized mixtures of 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole moieties. Catalyzed methodswould provide mainly the 4-vinyl substituted regioisomer. The mixturesof 4- and 5-vinyl substituted regioisomers may be separated byconventional chromatographic methods to provide the purified 4-vinylsubstituted regioisomers and the 5-vinyl substituted regioisomers. The5-vinyl substituted 1,2,3-triazole moiety cannot be prepared by acatalyzed method. The purified 4-vinyl substituted regioisomers and the5-vinyl substituted regioisomers may then be employed to prepare 4-vinylsubstituted and 5-vinyl substituted homopolymers and non-homopolymers

Chromatography is the collective term for a group of laboratorytechniques for the separation of mixtures. The techniques involvepassing a mixture dissolved in a mobile phase through a stationaryphase, which separates the analyte to be measured from other moleculesin the mixture and allows it to be isolated. Preparative chromatography,the preferred technique to be employed in this invention, separates thecomponents of a mixture for further use and is thus a form ofpurification. The various forms of chromatography are well known tothose of skill in the art. The most general technique for separatinglarge amounts of material is column chromatography. Columnchromatography is a separation technique in which the stationary bed iswithin a tube. The particles of the solid stationary phase or thesupport coated with a liquid stationary phase may fill the whole insidevolume of the tube (packed column) or be concentrated on or along theinside tube wall leaving an open, unrestricted path for the mobile phasein the middle part of the tube. Differences in rates of movement throughthe medium are calculated to different retention times of the sample.Another technique that may be employed is liquid chromatography, whichis a separation technique in which the mobile phase is a liquid. Liquidchromatography can be carried out either in a column or a plane. Liquidchromatography that generally utilizes very small packing particles anda relatively high pressure is referred to as high performance liquidchromatography (HPLC). In the HPLC technique, the sample is forcedthrough a column that is packed with irregularly or spherically shapedparticles or a porous monolithic layer (stationary phase) by a liquid(mobile phase) at high pressure. HPLC is generally divided into twodifferent sub-classes based on the polarity of the mobile and stationaryphases. The technique in which the stationary phase is more polar thanthe mobile phase is called normal phase liquid chromatography (NPLC) andthe opposite is called reversed phase liquid chromatography (RPLC).Reversed-phase chromatography is an elution procedure used in liquidchromatography in which the mobile phase is significantly more polarthan the stationary phase. The appropriate method and conditions ofchromatography to separate the mixtures of 4- and 5-substitutedregioisomers are well known in the art.

As set out above, the availability of various N-1 substituent optionsallows for the custom manufacturing of polymers with specific physicalproperty properties. For example when the N-1 substituent is n-C₈H₁₇,one obtains a hydrophobic functionalized mixture of 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole moieties. On the other hand,when the N-1 substituent is CH₂CH₂OH, CH₂CH₂OCH₂CH₂OH, or CH₂CH₂N(CH₃)₂,one obtains a hydrophilic functionalized mixture of 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole moieties.

Optionally, a free radical addition polymerization initiator may beemployed in the polymerization reaction. Non-limiting illustrativeexamples of free radical addition polymerization initiators include2,2′-azobis(2-methylpropionitrile) and benzoyl peroxide. A preferredfree radical addition polymerization initiator is 2,2′-azobis(2-methylpropionitrile).

Depending on the end application, one or more fillers may be included inthe compositions and usually are added for improved rheologicalproperties and stress reduction. Examples of suitable nonconductivefillers include alumina, aluminum hydroxide, silica, fused silica, fumedsilica, vermiculite, mica, wollastonite, calcium carbonate, titania,sand, glass, barium sulfate, zirconium, carbon black, organic fillers,and halogenated ethylene polymers, such as, tetrafluoroethylene,trifluoroethylene, vinylidene fluoride, vinyl fluoride, vinylidenechloride, and vinyl chloride. Examples of suitable conductive fillersinclude carbon black, graphite, gold, silver, copper, platinum,palladium, nickel, aluminum, silicon carbide, boron nitride, diamond,and alumina.

The filler particles may be of any appropriate size ranging from nanosize to several mm. The choice of such size for any particular end useis within the expertise of one skilled in the art. The filler may bepresent in an amount from 10 to 90% by weight of the total composition.More than one filler type may be used in a composition and the fillersmay or may not be surface treated. Appropriate filler sizes can bedetermined by the practitioner, but, in general, will be within therange of 20 nanometers to 100 microns.

Other materials, such as adhesion promoters (e.g. epoxides, silanes),dyes, pigments, and rheology modifiers may be added as desired for themodification of the final properties. Such materials and the amountsneeded are within the expertise of those skilled in the art.

The compounds of the present invention can be prepared according to theexamples set out below. The examples are presented for purposes ofdemonstrating, but not limiting, the preparation of the compounds andcompositions of this invention.

EXAMPLES

In accordance with the present invention, the following examples areprovided to illustrate preferred methods for preparing novel methods forthe ligation of azides and alkynes using 1,3-dipolar cycloadditionreactions to provide a functionalized mixture of 4- and 5-vinylsubstituted regioisomers of 1,2,3-triazole monomers, which may beconverted to a wide variety of useful functionalized mixture of 4- and5-vinyl substituted regioisomers of 1,2,3-triazole polymers.

Example 1 Synthesis of 2-(1-octyl-1H-1,2,3-triazol-4-yl)propan-2-ol

A 2-liter 4-neck round-bottom reaction flask was equipped with amechanical mixer, reflux condenser, heating mantle, temperature probeand temperature controller. The flask was charged with water (464grams), sodium azide (100.0 grams, 1.5382 mol), 2-methyl-3-butyn-2-ol(117.6 grams, 1.3984 mol) and 1-bromooctane (270.1 grams, 1.3984 mol). Acontinuous mild air purge was applied to sweep the contents of theflask. The set-point of the internal temperature controller wasinitially set to 95° C. The contents were mixed vigorously at 400 rpms.The reaction was heated to reflux and maintained at a temperaturebetween 92 and 97° C.; the temperature controller set-point was adjustedaccordingly. Reaction conversion was monitored via thin-layerchromatography using an ethyl acetate/hexane solvent system of 4/1 byvolume, respectively. After 24 hours of being heated at reflux, thereaction was discharged to a 2-liter separatory funnel to cool. Whilecooling, the reaction “phased out” to a clear yellow organic layer overa clear and colorless aqueous layer. The organic layer (productsolution) was collected and the bottom aqueous layer was discarded. Theproduct solution was diluted with 320 ml of ethyl acetate. Hexane (80ml) and silica gel (40 grams) were added to the mixture, which was thenstirred for 1 hour. The silica gel was removed by filtration leaving aclear yellow product solution. The solvent was then removed viaroto-evaporation over about 2 hours at 85-90° C. and ˜250 Torr. Theproduct was collected as a clear, yellow low-viscosity oil. Thestructure of this triazole was confirmed by NMR and LC-MS.

Example 2 Synthesis of 1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole

A 3 L 4-neck round bottom reaction flask was equipped with a mechanicalstirrer, temperature probe/controller, condenser and ice bath/heatingmantle. The flask was charged with2-(1-octyl-1H-1,2,3-triazol-4-yl)propan-2-ol (100 grams, 0.4184 mol) andpyridine (870.1 grams, 26.3 mol) at room temperature. The clear goldsolution was mixed for 5 minutes. A slow-addition funnel charged withPOCl₃ was mounted on the flask. The flask and contents were chilled to˜0° C. in the ice bath. POCl₃ (128.3 grams, 0.8368 mol) was addeddrop-wise while maintaining a reaction temperature </=5° C. At thisscale, the addition lasted ˜1.25 hrs and the reaction temperature rangedfrom about 2 to 5° C. The reaction flask was then fitted with a heatingmantle and the contents were mixed and heated to reflux for 3 hours at areaction temperature ˜120° C. By the end of 3 hours, the reaction was aclear dark-brown solution. The reaction solution was poured into a 2 Lseparatory funnel charged with ˜500 ml of ice. [Beware of heat generatedby the dissolution of HCl, a by-product of the reaction.] Time wasallowed for the contents of the separatory funnel to cool and“phase-out”. The top dark brown “oil” phase was then isolated. Thebottom dark-brown aqueous phase was extracted twice with 200 ml of ethylacetate per extraction. The oil phase and the extractions were combined,thereby forming the “product solution”. The product solution was washedrepeatedly with 500 mL of 1M HCl. After each wash, the pH of the washwater was measured. The acid washing step was repeated until the pH ofthe wash water matched the pH of the 1M HCl solution (˜0-1). A pH of 0-1was achieved by the end of the fourth wash in this example. The acidwashes were followed by a final wash using 300 mL of saturated sodiumbicarbonate solution. The pH of the final wash was ˜9. The productsolution was then collected, dried over 10 grams of magnesium sulfateand filtered. Removal of the solvent (˜250 Torr, 85° C. for 90 minutes)resulted in 81 grams of a thin dark amber oil. The structure of thistriazole was confirmed by NMR and LC-MS.

Example 3 Synthesis of Methyl3-(4-(2-hydroxypropan-2-yl)-1H-1,2,3-triazol-1-yl)propanoate (StandardProcedure With Catalyst/Organic Solvent)

A 1 liter 4-neck round-bottom reaction flask was equipped with amechanical mixer, reflux condenser, heating mantle, temperature probeand temperature controller. The flask was charged with water (162.4grams), sodium azide (40.0 grams, 0.6153 mol), sodium ascorbate (8.2grams, 0.0414 mol), and copper sulfate (2.2 grams, 0.0138 mol). Themixture was stirred to dissolve solids, resulting in a clear dark brownsolution. N,N dimethylformamide (DMF, 162.4 grams) was added and thesolution became a turbid orange dispersion. No observable changeoccurred with the addition of methyl-3-bromopropionate (23.1 grams,0.1383 mol). However, the reaction became a light gold color when2-methyl-3-butyn-2-ol (17.45 grams, 0.2075 mol) was added as the lastreactant. The dispersion was heated with mixing for 20 hours at ˜70° C.The opaque dark brown reaction was discharged to a reparatory funnel tocool. After the addition of dichloromethane, water, and brine (200 mleach), the reaction separated to a dark red aqueous phase over a lightbrown organic phase. The organic phase was collected and set aside.Three extractions each using 200 mL of dichloromethane were performed onthe aqueous phase of the reaction. More brine was added as needed to aidin phase separation. The dichloromethane solution from the firstextraction was light yellow and hazy while the final was clear andcolorless. The initial organic phase and the extractions were combinedand washed three times each with 250 ml of water. After washing, thehazy golden yellow organic phase was dried over 10 grams of magnesiumsulfate. The mixture was filtered and the final solution wasconcentrated on a roto-evaporator at about 80° C. The product wascollected as a clear red-orange low-viscosity oil. The structure of thistriazole was confirmed by NMR and LC-MS.

Example 4 Synthesis of methyl3-(4-(2-hydroxypropan-2-yl)-1H-1,2,3-triazol-1-yl)propanoate (GreenProcedure—No Catalyst/Organic Solvent)

A 500 ml 4-neck round-bottom reaction flask was equipped with amechanical mixer, reflux condenser, hot oil bath, temperature probe andtemperature controller. The flask was charged with water (85 grams),sodium azide (20.0 grams, 0.0.3076 mol), methyl-3-bromopropionate (46.71grams, 0.2797 mol), and 2-methyl-3-butyn-2-ol (23.53 grams, 0.2797 mol).A mild air-flow was applied to flush the flask for the course of thereaction. The resulting dispersion was placed in a hot oil bath andheated to reflux with mixing for 24 hours at about 94 to ˜102° C. Thehazy gold-brown reaction solution was discharged to a separatory funnelto cool. Water (340 ml) was also charged to the funnel. The reactionfailed to phase out into separate organic and aqueous layers. Four ethylacetate extractions of 100 ml each were performed to obtain product fromthe homogeneous solution. Based on thin-layer chromatography eluted withethyl acetate, the first two extractions contained product and werecombined to form a product solution. The product solution was thenwashed three times with 200 ml of de-ionized water per wash. The darkgold organic phase was then dried over 10 grams of magnesium sulfate andfiltered. Methanol (50 ml) was stirred into the 250 ml ethylacetate-product solution followed by 15 grams of silica gel. Theresulting mixture was stirred for one hour, filtered and thenconcentrated. The product was collected as a dark brown oil. Thestructure of this triazole in isomeric forms was confirmed by NMR andLC-MS.

Example 5 Synthesis of methyl3-(4-(prop-1-en-2-yl)-1H-1,2,3-triazol-1-yl)propanoate

A 100 mL 4-neck round bottom reaction flask was equipped with a magneticstir bar, thermometer, temperature controller, condenser, oil bath andsalt/ice bath. The flask was charged with methyl3-(4-(2-hydroxypropan-2-yl)-1H-1,2,3-triazol-1-yl)propanoate (5.0 grams,0.0235 mol) and pyridine (48.9 grams, 0.6182 mol) at room temperature.The resulting clear gold solution was mixed for 5 minutes. Aslow-addition funnel charged with POCl₃ was mounted on the flask. Theflask and contents were chilled to −7° C. in the salt/ice bath. POCl₃(7.2 grams, 0.0470 mol) was added drop-wise while a reaction temperature</=10° C. was maintained. At this scale, the addition lasted ˜0.5 hrsand the reaction temperature ranged from −7 to 10° C. By the end of theaddition, the contents of the flask changed from a clear gold solutionto a thick gold-yellow slurry. The reaction flask was then placed into ahot oil bath and the contents were mixed and heated to reflux for 2hours at a reaction temperature ˜110 to 122° C. By the end of theheating process, the reaction was a clear red-brown solution, which wasallowed to cool over night. During cooling, crystals formed on thebottom of the flask. The contents of the flask were then discharged to aseparatory funnel filled with ice. [Beware of heat generated by thedissolution of HCl, a by-product of the reaction.] Approximately 200 mleach of water and methylene chloride were added to the funnel aftercooling to promote separation of the aqueous and organic layers.However, the darkness of the layers precluded observation of theseparation. The reaction solution was then stripped of pyridine (andmethylene chloride) on the roto-evaporator at 80-90° C. Once again, 200ml each of both water and methylene chloride were added, the layers wereobserved to separate and the organic layer was collected. The organiclayer was then washed with 500 ml of 1M hydrochloric acid solution,which changed the organic solution from dark brown to clear amber. Theacid wash was followed by a 300 ml saturated sodium bicarbonate wash.The reaction solution was then dried over 10 grams of magnesium sulfate,filtered and concentrated on a roto-evaporator. The product wascollected as a dark brown opaque oil and the structure was confirmed byboth NMR and HPLC.

Example 6 Synthesis of 1-hydroxyethyl-1,2,3-triazol-4-yl)propan-2-ol

A 500 ml 4-neck round-bottom reaction flask was equipped with amechanical mixer, reflux condenser, heating mantle, temperature probeand temperature controller. The flask was charged with water (125grams), sodium azide (39.97 grams, 0.6148 mol), 2-methyl-3-butyn-2-ol(47.01 grams, 0.5589 mol) and 2-chloroethanol (45.0 grams, 0.5589 mol).A continuous air purge was applied to sweep the contents of the flask.The set point of the internal temperature controller was set to about110° C. and the contents were mixed vigorously at 400 rpms. The reactionwas heated to reflux and maintained at a temperature between 92 and 105°C. Reaction conversion was monitored via thin-layer chromatography usingan ethyl acetate/hexane solvent system of 4/1 by volume, respectively.After 24 hours of refluxing, the reaction color changed from a cloudylight gray to a hazy dark gold color. The reaction was stopped and thebulk of the water was removed via roto-evaporation (2 hours @ 85-90° C.and ˜250 Torr). The crude product mixture was dissolved in 750 ml ofacetone, which promoted precipitation of salts. The salts were filteredfrom the product solution three times as they continued to form. Whenclear, the final solution was then poured through 55 grams of silica gelconstructed as a pad in a Buchner funnel. The product was concentratedon a roto-evaporator and collected as a clear gold oil. The structure ofthis triazole was confirmed by NMR and LC-MS.

Example 7 Synthesis of2-(4-prop-1-en-2-yl)-1H-1,2,3-triazol-1-yl)ethanol

A 1 L 4-neck round bottom reaction flask was equipped with a mechanicalstirrer, thermometer, temperature controller, condenser, oil bath andsalt/ice bath. The flask was charged with1-hydroxyethyl-1,2,3-triazol-4-yl)propan-2-ol (40.0 grams, 0.2336 mol)and pyridine (486 grams, 6.1437 mol) at room temperature. The cloudygold-yellow solution was mixed for 5 minutes. A slow-addition funnelcharged with POCl₃ was mounted on the flask. The flask and contents werechilled to about 1° C. in the salt/ice bath. POCl₃ (71.64 grams, 0.4672mol) was added drop-wise while maintaining a reaction temperature </=10°C. At this scale, the addition lasted 1.25 hrs and the reactiontemperature ranged from about −5 to 7° C. By the end of the addition,the contents of the flask changed to an orange solution with whitesalts. The reaction flask was then placed into a hot oil bath and thecontents were mixed and heated to reflux for 2 hours at a reactiontemperature ˜120° C. By the end of heating, the reaction was a cleardark brown solution, which was allowed to cool. The contents of theflask were then discharged to a 2 L separatory funnel filled with ice.[Beware of heat generated by the dissolution of HCl, a by-product of thereaction.] The reaction solution was then extracted twice with 250 mleach of ethyl acetate. The ethyl acetate fractions both phased-out wellover the aqueous layers within five minutes. The extractions were thencombined and washed four times with 500 ml each of 1M HCl. By the end ofthe fourth wash, the pH of the washes had dropped from 6 to 0,indicating that most of the pyridine had been removed. The acid washeswere followed by a 300 ml saturated sodium bicarbonate wash. The hazygold reaction solution was isolated and dried over 10 grams of magnesiumsulfate, filtered and concentrated on a roto-evaporator at 85° C. Theproduct was collected as a clear gold oil and the structure wasconfirmed by NMR and HPLC.

Example 8 Synthesis of2-(1-(2-(2-hydroxyethoxy)ethyl)-1H-1,2,3-triazol-5-yl)propan-2-ol

A 1 L 4-neck round-bottom reaction flask was equipped with a mechanicalmixer, reflux condenser, heating mantle, temperature probe andtemperature controller. The flask was charged with water (214 grams),sodium azide (57.4 grams, 0.8830 mol), 2-methyl-3-butyn-2-ol (75.5grams, 0.0.8028 mol) and 2-(2-chloroethoxy)-ethanol (100.0 grams, 0.8028mol). A continuous air purge was applied to sweep the contents of theflask. The set point of the internal temperature controller was set to110° C. and the contents were mixed vigorously (400 rpms). The reactionwas heated to reflux and maintained at a temperature between 92 and 108°C. Reaction conversion was monitored via thin-layer chromatography usingan ethyl acetate/hexane solvent system of 4/1 by volume, respectively.After 24 hours of heating, the reaction color changed from a cloudylight gray to a hazy dark gold color. The bulk of the water was removedvia roto-evaporation for ˜2 hours at 85-90° C. and ˜250 Torr. The crudeproduct mixture was dissolved in 700 ml of acetone, which promotedprecipitation of salt. The salts were filtered from the product solutionthree times as they continued to form. The final clear solution was thenpoured through 55 grams of silica gel constructed as a pad in a Buchnerfunnel. The product was concentrated on a roto-evaporator and collectedas a clear gold oil. The structure of this triazole was confirmed by NMRand LC-MS.

Example 9 Synthesis of2-(2-(5-(prop-1-en-2-yl)-1H-1,2,3-triazol-1-yl)ethoxy)ethanol

A 1 L 4-neck round bottom reaction flask was equipped with a mechanicalstirrer, thermometer, temperature controller, condenser, oil bath andsalt/ice bath. The flask was charged with2-(1-(2-(2-hydroxyethoxy)ethyl)-1H-1,2,3-triazol-5-yl)propan-2-ol (40.0grams, 0.1859 mol) and pyridine (386.7 grams, 4.8892 mol) at roomtemperature. The cloudy gold-yellow solution was mixed for 5 minutes. Aslow-addition funnel charged with POCK was mounted on the flask. Theflask and contents were chilled to 2° C. in the salt/ice bath. POCl₃(57.00 grams, 0.3718 mol) was added dropwise while the reactiontemperature was maintained at </=5° C. The addition lasted 1.3 hrs andthe reaction temperature ranged from about −2 to 2° C. By the end of theaddition, the contents of the flask changed to a white mixture. Thereaction flask was then placed into a hot oil bath and the contents weremixed and heated to reflux for 3 hours at a reaction temperature ˜119°C. By the end of heating, the reaction was a clear dark brown solution.In an effort to remove pyridine before work-up, a Dean-Stark trap wasfitted to the reflux condenser whereby 186 ml of a clear and colorlessliquid was collected over 30 minutes. The product solution was allowedto cool over night. The following day, the contents of the flask weredischarged to a 2 L separatory funnel filled with ice. [Beware of heatgenerated by the dissolution of HCl, a by-product of the reaction.] Thereaction solution was then extracted twice with 250 ml each of ethylacetate. The extractions were then combined and washed four times with500 ml each of 1M HCl. By the end of the fourth wash, the solution haddropped from pH 6 to pH 0, thereby indicating that most of the pyridinehad been removed. The acid washes were followed by a 300 ml saturatedsodium bicarbonate wash. The product solution was isolated and driedover 10 grams of magnesium sulfate, filtered and concentrated on aroto-evaporator at 85° C. The product was collected as a dark brown oiland the structure was confirmed by both NMR and HPLC.

Example 10 Synthesis of2-(1-(2-(dimethylamino)ethyl)-1H-1,2,3-triazol-5-yl)propan-2-ol

A 2 L 4-neck round-bottom reaction flask was equipped with a mechanicalmixer, reflux condenser, heating mantle, temperature probe andtemperature controller. The flask was charged with water (464 grams),sodium azide (100 grams, 1.53 mol), 2-methyl-3-butyn-2-ol (117.6 grams,1.398 mol) and (dimethylamino)ethylchloride.HCl (201.4 grams, 1.398mol). A continuous air purge was applied to sweep the contents of theflask. The set point of the internal temperature controller was set to110° C. and the contents were mixed vigorously (400 rpms). The reactionwas heated to reflux and was maintained at a temperature between 81 and103° C. After 24 hours of heating, the reaction color changed from adark orange to a hazy dark yellow color. The crude product mixture wasdissolved in 1000 ml of acetone, which promoted precipitation of salts.Salts were filtered from the product solution three times as theycontinued to form. The final clear solution was then poured throughsilica gel constructed as a pad in a Buchner funnel. The product wasconcentrated on a roto-evaporator and collected as a thick hazy amberoil. The structure of this triazole was confirmed by both NMR and LC-MS.

Example 11 Synthesis ofN,N-dimethyl-2-(5-(prop-1-en-2-yl)-1H-1,2,3-triazol-1-yl)ethanamine

A 1 L 4-neck round bottom reaction flask was equipped with a mechanicalstirrer, thermometer, temperature controller, condenser, oil bath andsalt/ice bath. The flask was charged with2-(1-(2-(dimethylamino)ethyl)-1H-1,2,3-triazol-5-yl)propan-2-ol (40grams, 0.2017 mol) and pyridine (419.6 grams, 5.3047 mol) at roomtemperature. The solution was mixed for 5 minutes. A slow-additionfunnel charged with POCl₃ was mounted on the flask and the contents werechilled in a salt/ice bath. POCl₃ (61.8 grams, 0.4030 mol) was addeddrop-wise while maintaining a reaction temperature </=10° C. Thereaction flask was then placed into a hot oil bath and the contents weremixed and heated to reflux for 2 hours at a reaction temperature ˜120°C. After heating, the reaction was allowed to cool and the contents ofthe flask were discharged to a 2 L separatory funnel filled with ice[beware of heat generated by the dissolution of HCl, a by-product of thereaction]. The reaction solution was then extracted twice with 250 mleach of ethyl acetate. The extractions were then combined and washedfour times with 500 ml each of 1M HCl. By the end of the fourth wash,the pH of the wash dropped from 6 to pH 0, thereby indicating that mostof the pyridine had been removed. The acid washes were followed by a 300ml saturated sodium bicarbonate wash. The reaction solution was isolatedand dried over 10 grams of magnesium sulfate, filtered and concentratedon a roto-evaporator at 80° C. The product was collected and submittedfor structure confirmation by both NMR and HPLC.

Example 12 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole]

A mixture of 2,2′-azobis-2-methylpropionitrile (27.0 mg, 0.122 mmol) andthe triazole monomer (4.00 g, 18.1 mmol) was bubbled with nitrogen atroom temperature for at least 10 minutes, and heated at 70° C. for 4hours. The crude polymerization mixture was then precipitated twice inhexanes. The hexanes were then decanted and the remaining pure polymerwas dried under vacuum for 12 hours. The structure of the polymer wasconfirmed by GPC, NMR, and DSC.

Example 13 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-alt-maleic anhydride]

52.5 g Maleic anhydride, 119.0 g triazole monomer, and 214 ml methylethyl ketone (MEK) was added into a one-liter five-neck resin kettle,fitted with a Teflon anchor agitator, a nitrogen purge dip tube, athermocouple, a reflux condenser, and an adapter. The reactor was purgedwith nitrogen throughout the experiment and heated to 75° C. After thetemperature reached 75° C., the reaction mixture was further bubbledwith nitrogen for ½ hour. Then 2.4 g of AIBN in 25 ml MEK were addedinto the kettle. After one hour and two hour, two aliquots of 1.2 g AIBNin 10 ml MEK were charged into the systems respectively. The reactionwas continued for another 2 hours, and then the crude polymerizationmixture was precipitated twice in methanol/hexanes. The solvents werethen removed by filtration and the remaining pure polymer was driedunder vacuum for 12 hours. The structure of the polymer was confirmed byGPC, NMR, DSC, and TGA.

Example 14 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-alt-maleic diacid]

A mixture of 1.0 g ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-alt-maleic anhydride]and 100 ml 0.1 M NaOH aqueous solution was heated at 60° C. for fourhours, at which point the mixture became homogenous. The pH of thereaction was then adjusted to pH=7 by using 0.1 M HCL aqueous solution.Adjusting the pH below 5.5 would cause the polymer to precipitate. Thestructure of the water-soluble polymer was confirmed by GPC, NMR andDLS.

Example 15 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-N-vinyl-pyrrolidone]

A mixture of 2,2′-azobis-2-methylpropionitrile (120 mg, 0.73 mmol), thetriazole monomer (2.70 g, 12.2 mmol), N-vinyl-pyrrolidone (0.30 g, 2.69mmol), and iso-propanol (4.21 g, 70.0 mmol) was bubbled with nitrogenline for 10 minutes, and heated at 70° C. for 6 hours. The viscous crudepolymerization mixture was then precipitated twice in hexanes. Thesolvents were then removed by filtration and the remaining pure polymerwas dried under vacuum for 12 hours. The structure of the polymer wasconfirmed by GPC, NMR, and DSC.

Example 16 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-N-vinyl-caprolactam]

A mixture of 2,2′-azobis-2-methylpropionitrile (40.0 mg, 0.244 mmol),the triazole monomer (0.42 g, 1.90 mmol), N-vinyl-caprolactam and (4.08g, 29.3 mmol), and ethanol (4.80 g, 104 mmol) was bubbled with nitrogenat room temperature for at least 10 minutes, and heated at 70° C. for 9hours. The viscous crude polymerization mixture was then precipitatedtwice in hexanes. The solvents were then removed by filtration and theremaining pure polymer was dried under vacuum for 12 hours. Thestructure of the polymer was confirmed by GPC and NMR.

Example 17 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-N,N-dimethylaminoethylmethacrylate]

A mixture of 2,2′-azobis-2-methylpropionitrile (31.4 mg, 0.191 mmol),the triazole monomer (0.40 g, 1.81 mmol), and N,N′-dimethylaminoethylmethacrylate (4.00 g, 25.4 mmol) was bubbled with nitrogen line for 10minutes, and heated at 70° C. for 3.5 hours. The viscous crudepolymerization mixture was then precipitated twice in hexanes. Thesolvents were then removed by filtration and the remaining pure polymerwas dried under vacuum for 12 hours. The structure of the polymer wasconfirmed by GPC and NMR.

Example 18 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-N,N-dimethylamino-propylmethaerylamide]

A mixture of 2,2′-azobis-2-methylpropionitrile (30.4 mg, 0.185 mmol),the triazole monomer (0.40 g, 1.81 mmol), and N,N′-dimethylaminoethylmethacrylate (4.00 g, 23.5 mmol) was bubbled with nitrogen at roomtemperature for at least 10 minutes, and heated at 70° C. for 4.5 hours.The viscous crude polymerization mixture was then precipitated twice inhexanes. The solvents were then removed by filtration and the remainingpure polymer was dried under vacuum for 12 hours. The structure of thepolymer was confirmed by GPC and NMR.

Example 19 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-acrylic acid]

A mixture of 2,2′-azobis-2-methylpropionitrile (32.1 mg, 0.195 mmol),the triazole monomer (0.40 g, 1.81 mmol), and acrylic acid (4.00 g, 55.5mmol) was bubbled with nitrogen at room temperature for at least 10minutes, and heated at 70° C. for 1.5 hours. The resulting white solidpolymer was then precipitated twice in methanol and dried under vacuumfor 12 hours.

Example 20 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-styrene]

A mixture of 2,2′-azobis-2-methylpropionitrile (30.8 mg, 0.188 mmol),the triazole monomer (0.80 g, 3.62 mmol), and styrene (4.00 g, 38.4mmol) was bubbled with nitrogen line for 10 minutes, and heated at 70°C. for 7.0 hours. The viscous crude polymerization mixture was thenprecipitated twice in methanol. The solvents were then removed byfiltration and the remaining pure polymer was dried under vacuum for 12hours. The structure of the polymer was confirmed by GPC, NMR, and DSC.

Example 21 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-methyl acrylate]

A mixture of 2,2′-azobis-2-methylpropionitrile (30.5 mg, 0.186 mmol),the triazole monomer (0.80 g, 3.62 mmol), and methyl acrylate (4.00 g,46.5 mmol) was bubbled with nitrogen at room temperature for 10 minutes,and heated at 70° C. for 3.0 hours. The viscous crude polymerizationmixture was then precipitated twice in methanol. The solvents were thenremoved by filtration and the remaining pure polymer was dried undervacuum for 12 hours. The structure of the polymer was confirmed by GPC,NMR, and DSC.

Example 22 Synthesis ofpoly[1-octyl-4-(prop-1-en-2-yl)-1H-1,2,3-triazole-co-methylmethacrylate]

A mixture of 2,2′-azobis-2-methylpropionitrile (34.7 mg, 0.212 mmol),the triazole monomer (0.80 g, 3.62 mmol), and methyl methacrylate (4.00g, 40.0 mmol) was bubbled with nitrogen line for 10 minutes, and heatedat 70° C. for 3.0 hours. The viscous crude polymerization mixture wasthen precipitated twice in methanol. The solvents were then removed byfiltration and the remaining pure polymer was dried under vacuum for 12hours. The structure of the polymer was confirmed by GPC, NMR, and DSC.

While a number of embodiments of this invention have been represented,it is apparent that the basic construction can be altered to provideother embodiments that utilize the invention without departing from thespirit and scope of the invention. All such modifications and variationsare intended to be included within the scope of the invention as definedin the appended claims rather than the specific embodiments that havebeen presented by way of example.

We claim:
 1. An alcoholic mixture of 4- and 5-substituted regioisomersof 1,2,3-triazole moieties.
 2. The alcoholic mixture according to claim1, wherein the mixture is represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.3. The alcoholic mixture according to claim 1, wherein the mixture isrepresented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about
 500. 4.An adhesive, coating, encapsulation, personal care, oilfield, membrane,agricultural, or cleaning composition comprising an alcoholic mixture of4- and 5-substituted regioisomers of 1,2,3-triazole moieties.
 5. Thecomposition according to claim 4, wherein the mixture is represented bythe structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.6. The composition according to claim 4, wherein the mixture isrepresented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about
 500. 7.An 4-alcoholic substituted 1,2,3-triazole moiety represented by thestructure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 2 to about
 500. 8.An adhesive, coating, encapsulation, personal care, oilfield, membrane,agricultural, or cleaning composition comprising a 4-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.9. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a 4-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 2 to about 500.10. An 5-alcoholic substituted 1,2,3-triazole moiety represented by thestructure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.11. An 5-alcoholic substituted 1,2,3-triazole moiety represented by thestructure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about 500.12. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a 5-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.13. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a 5-alcoholicsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about 500.14. A mixture of 4- and 5-vinyl substituted regioisomers of1,2,3-triazole moieties.
 15. The vinyl mixture according to claim 14,wherein the mixture is represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.16. The vinyl mixture according to claim 14, wherein the mixture isrepresented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about 500.17. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a mixture of4- and 5-vinyl substituted regioisomers of 1,2,3-triazole moieties. 18.The composition according to claim 17, wherein the mixture isrepresented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.19. The composition according to claim 17, wherein the mixture isrepresented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about 500.20. A 4-vinyl substituted 1,2,3-triazole moiety represented by thestructure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 2 to about 500.21. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a 4-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.22. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a 4-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about 500.23. A 5-vinyl substituted 1,2,3-triazole moiety represented by thestructure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.24. A 5-vinyl substituted 1,2,3-triazole moiety represented by thestructure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about 500.25. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a 5-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond.26. An adhesive, coating, encapsulation, personal care, oilfield,membrane, agricultural, or cleaning composition comprising a 5-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁ and R₂ are independently selected from the group consistingof hydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; R₅ is selected from the group consistingof functionalized and unfunctionalized alkyl, cycloalkyl, alkenyl, andaryl groups, wherein any of the before mentioned groups may be with orwithout heteroatoms; and x is an integer ranging from 1 to about 500.27. A homopolymer of a mixture of 4- and 5-vinyl substitutedregioisomers of 1,2,3-triazole moieties.
 28. The homopolymer accordingto claim 27, wherein the homopolymer is represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond;and y is an integer ranging from 2 to about 10,000.
 29. An adhesive,coating, encapsulation, personal care, oilfield, membrane, agricultural,or cleaning composition comprising a homopolymer of a mixture of 4- and5-vinyl substituted regioisomers of 1,2,3-triazole moieties.
 30. Thecomposition according to claim 29, wherein the homopolymer isrepresented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amities, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond;and y is an integer ranging from 2 to about 10,000.
 31. An adhesive,coating, encapsulation, personal care, oilfield, membrane, agricultural,or cleaning composition comprising a homopolymer of a 4-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond;and y is an integer ranging from 2 to about 10,000.
 32. A homopolymer ofa 5-vinyl substituted 1,2,3-triazole moiety represented by thestructure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond;and y is an integer ranging from 2 to about 10,000.
 33. An adhesive,coating, encapsulation, personal care, oilfield, membrane, agricultural,or cleaning composition comprising a homopolymer of a 5-vinylsubstituted 1,2,3-triazole moiety represented by the structure:

wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond;and y is an integer ranging from 2 to about 10,000.
 34. Anon-homopolymer of a mixture of 4- and 5-vinyl substituted regioisomersof 1,2,3-triazole moieties with a different polymerizable reactantmoiety, wherein the non-homopolymer is a random, blocked, or alternatingpolymer.
 35. The non-homopolymer according to claim 34, wherein thenon-homopolymer is represented by the structure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂ and R₃ are independently selected from the group consisting ofhydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; and R₄ is selected from the groupconsisting of a direct bond, carboxylic acids, esters, amides,anhydrides, aldehydes, ketones, ethers, amines, alcohols, and thiols;with the proviso that when R₃ is hydrogen, R₄ is a direct bond; and yand z are integers independently ranging from about 2 to about 10,000,wherein the non-homopolymer is a random, blocked, or alternatingpolymer.
 36. The non-homopolymer according to claim 35, wherein M isbased upon a different polymerizable reactant moiety selected from thegroup consisting of anhydrides, vinyl pyrrolidones, vinyl caprolactams,acrylates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinylimidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinylsulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allylalcohols, vinyl ethers, and mixtures thereof.
 37. An adhesive, coating,encapsulation, personal care, oilfield, membrane, agricultural, orcleaning composition comprising a non-homopolymer of a mixture of 4- and5-vinyl substituted regioisomers of 1,2,3-triazole moieties with adifferent polymerizable reactant moiety, wherein the non-homopolymer isa random, blocked, or alternating polymer.
 38. The composition accordingto claim 37, wherein the non-homopolymer is represented by thestructure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂, and R₃ are independently selected from the group consisting ofhydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; and R₄ is selected from the groupconsisting of a direct bond, carboxylic acids, esters, amides,anhydrides, aldehydes, ketones, ethers, amines, alcohols, and thiols;with the proviso that when R₃ is hydrogen, R₄ is a direct bond; and yand z are integers independently ranging from about 2 to about 10,000,wherein the non-homopolymer is a random, blocked, or alternatingpolymer.
 39. A non-homopolymer of a 4-vinyl substituted 1,2,3-triazolemoiety with a different polymerizable reactant moiety, wherein thenon-homopolymer is a random, blocked, or alternating polymer, whereinthe non-homopolymer is represented by the structure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂, and R₃ are independently selected from the group consisting ofhydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; and R₄ is selected from the groupconsisting of a direct bond, carboxylic acids, esters, amides,anhydrides, aldehydes, ketones, ethers, amines, alcohols, and thiols;with the proviso that when R₃ is hydrogen, R₄ is a direct bond; and yand z are integers independently ranging from about 2 to about 10,000,wherein the non-homopolymer is a random, blocked, or alternatingpolymer.
 40. The non-homopolymer according to claim 39, wherein M isbased upon a different polymerizable reactant moiety selected from thegroup consisting of anhydrides, vinyl pyrrolidones, vinyl caprolactams,acrylates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinylimidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinylsulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allylalcohols, vinyl ethers, and mixtures thereof.
 41. An adhesive, coating,encapsulation, personal care, oilfield, membrane, agricultural, orcleaning composition comprising a non-homopolymer of a 4-vinylsubstituted 1,2,3-triazole moiety with a different polymerizablereactant moiety, wherein the non-homopolymer is a random, blocked, oralternating polymer, wherein the non-homopolymer is represented by thestructure:

wherein M is based upon a different polymerizable reactant moiety, R₁,R₂, and R₃ are independently selected from the group consisting ofhydrogen, functionalized and unfunctionalized alkyl, cycloalkyl,alkenyl, and aryl groups, wherein any of the before mentioned groups maybe with or without heteroatoms; and R₄ is selected from the groupconsisting of a direct bond, carboxylic acids, esters, amides,anhydrides, aldehydes, ketones, ethers, amities, alcohols, and thiols;with the proviso that when R₃ is hydrogen, R₄ is a direct bond; and yand z are integers independently ranging from about 2 to about 10,000,wherein the non-homopolymer is a random, blocked, or alternatingpolymer.
 42. A non-homopolymer of a 5-vinyl substituted 1,2,3-triazolemoiety with a different polymerizable reactant moiety, wherein thenon-homopolymer is a random, blocked, or alternating polymer, whereinthe non-homopolymer is represented by the structure:

wherein M is based upon a different polymerizable reactant moiety,wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond;and y and z are integers independently ranging from about 2 to about10,000, wherein the non-homopolymer is a random, blocked, or alternatingpolymer.
 43. The non-homopolymer according to claim 42, wherein M isbased upon a different polymerizable reactant moiety selected from thegroup consisting of anhydrides, vinyl pyrrolidones, vinyl caprolactams,acrylates, styrenes, maleimides, maleates, fumarates, cinnamyls, vinylimidazoles, vinyl pyridines, vinyl acetates, acrylamides, vinylsulfones, vinyl carbonates, vinyl silanes, vinyl acrylamides, allylalcohols, vinyl ethers, and mixtures thereof.
 44. An adhesive, coating,encapsulation, personal care, oilfield, membrane, agricultural, orcleaning composition comprising a 5-vinyl substituted 1,2,3-triazolemoiety with a different polymerizable reactant moiety, wherein thenon-homopolymer is a random, blocked, or alternating polymer, whereinthe non-homopolymer is represented by the structure:

wherein M is based upon a different polymerizable reactant moiety,wherein R₁, R₂, and R₃ are independently selected from the groupconsisting of hydrogen, functionalized and unfunctionalized alkyl,cycloalkyl, alkenyl, and aryl groups, wherein any of the beforementioned groups may be with or without heteroatoms; and R₄ is selectedfrom the group consisting of a direct bond, carboxylic acids, esters,amides, anhydrides, aldehydes, ketones, ethers, amines, alcohols, andthiols; with the proviso that when R₃ is hydrogen, R₄ is a direct bond;and y and z are integers independently ranging from about 2 to about10,000, wherein the non-homopolymer is a random, blocked, or alternatingpolymer.